Phenylphosphinic Acid Research Articles

Multifunctional buried interface engineering via phenyl-phosphonic acid for efficient and stable SnO2-based planar perovskite solar cells

Tin dioxide (SnO2) is widely used as an electron transport layer (ETL) in efficient and stable perovskite solar cells (PSCs) due to its excellent optoelectronic properties and low-temperature solution preparation process. However, SnO2 ETLs fabricated by the conventional solution method have many defects, among which Sn dangling bonds (i.e., oxygen vacancies) are particularly prominent. Herein, a simple buried interface engineering is employed to introduce phenyl-phosphinic acid (PPA) into the surface of SnO2 film for the preparation of highly efficient PSCs. A series of test results have shown that the phosphate group (PO) in PPA can not only passivate oxygen vacancy defects on the surface of SnO2, but also improve the film-forming quality of the upper perovskite, thereby exhibiting better photoelectric conversion efficiency (PCE) and stability. Ultimately, the optimized device achieves a maximum PCE of 22.81 %, an improvement of about 15 % over the control device (19.82 %). Meanwhile, the nonencapsulated device based on SnO2-PPA ETL shows much better storage and light stability than the control SnO2.

Ionic Liquid-Based Extraction Strategy for the Efficient and Selective Recovery of Scandium.

The recovery of scandium (Sc) from highly acidic industrial effluents is currently hindered by the use of large quantities of flammable and toxic organic solvents. This study developed an extraction system using ionic liquids (ILs) and phenylphosphinic acid (PPAH) as diluents and an extractant, respectively, to selectively recover Sc from the aqueous phase. The effect of IL chemical structure, aqueous pH and temperature on the extraction of Sc was systematically investigated and the findings revealed that ILs with longer alkyl side chains had reduced Sc extraction ability due to the presence of continuous nonpolar domains formed by the self-aggregation of the IL alkyl side chain. The IL/PPAH system maintained high extraction ability toward Sc across a wide temperature range (288 K to 318 K) and the extraction efficiency of Sc could be improved significantly by increasing the aqueous pH. The extraction process involved proton exchange, resulting in the formation of a metal-ligand complex (Sc(PPA)3).

Comprehensive Biosafety Profile of Carbomer-Based Hydrogel Formulations Incorporating Phosphorus Derivatives.

Determining the safety of a newly developed experimental product is a crucial condition for its medical use, especially for clinical trials. In this regard, four hydrogel-type formulations were manufactured, all of which were based on carbomer (Blank-CP940) and encapsulated with caffeine (CAF-CP940), phosphorus derivatives (phenyl phosphinic (CAF-S1-CP940) and 2-carboxyethyl phenyl phosphinic acids (CAF-S2-CP940)). The main aim of this research was to provide a comprehensive outline of the biosafety profile of the above-mentioned hydrogels. The complex in vitro screening (cell viability, cytotoxicity, morphological changes in response to exposure, and changes in nuclei morphology) on two types of healthy skin cell lines (HaCaT-human keratinocytes and JB6 Cl 41-5a-murine epidermal cells) exhibited a good biosafety profile when both cell lines were treated for 24 h with 150 μg/mL of each hydrogel. A comprehensive analysis of the hydrogel's impact on the genetic profile of HaCaT cells sustains the in vitro experiments. The biosafety profile was completed with the in vivo and in ovo assays. The outcome revealed that the developed hydrogels exerted good biocompatibility after topical application on BALB/c nude mice's skin. It also revealed a lack of toxicity after exposure to the hen's chicken embryo. Further investigations are needed, regarding the in vitro and in vivo therapeutic efficacy and safety for long-term use and potential clinical translatability.

Syntheses and Spectroscopic Characterization of Selected Methyl Quinolinylphosphonic and Quinolinylphosphinic Acids; Rationalized based on DFT Calculation

Abstract: The quinoline derivatives arouse interest due to their broad spectrum of activity. The phosphorus compounds under investigation, quinolinylphosphonic and -phosphinic acids and aminophenylphosphonic and -phosphinic acids, possess potent bioactive properties, mimicking amino acids, phosphate esters, anhydrides, or carboxylate groups in enzymes. Despite its potential value, there is no reported example of quinolinylphosphonic or - phosphinic acids with phosphonic or phosphinic functional groups connected directly to the benzene ring in quinoline constitution. The selected quinoline derivatives have been synthesized by adopting the Skraup-Doebner-Von Miller reaction. To this end, the syntheses of aminophenylphosphonic and -phosphinic acids were conducted and afforded the target products with high yield. All structures have been proven by the combination of NMR, IR, MS, and HRMS techniques and were rationalized based on DFT calculation. The structures of triphenylphosphane oxide (TPO), diphenylphosphosphinic acid (1c), (tert-butyl)phenylphosphinic acid (1d) and bis(3-nitrophenyl)phosphinic acid (2c) were determined by single-crystal X-ray diffraction measurements. The Hirshfeld surface analyses for 1c, 1d and 2c were performed to analyze the intermolecular interactions in their crystal structures. According to our findings, the presence of numerous intermolecular PO•••H, NO•••H, and CH•••O contacts stabilizes the crystal structures. The NO•••H interactions manifest in the IR spectrum of 2c crystal as a narrow band with a maximum at 3088 cm-1. The PO•••H intermolecular interactions are attributed to a weak experimental band at 1288 cm-1.

Study of the effect of phosphorylated carboxylic acids new derivatives on the main behavioral disorders in rats in the valproate model of autism

BACKGROUND: Due to the increasing frequency of autism in the population, the complexity of behavioral symptoms, and the need for long-term therapy, it is important to find new safe drugs for the correction of behavioral disorders.
 AIM: Studying the possibility of correcting behavioral changes characteristic of autism in rats in the valproate model of autism using new derivatives of phosphorylated carboxylic acids.
 MATERIAL AND METHODS: The possibility of correcting behavioral disorders in male and female rats in the valproate model of autism was studied with intraperitoneal administration (7 days) of new derivatives from the group of phosphorylated acetohydrazides (B2, C5) and thiosemicarbazide (T8) in doses of 1/100 LD50 on behavioral tests “Elevated Plus Maze”, “Burying Balls”, “Extended Open Field”. Statistical processing was carried out in the GraphPad prism 8.0.1 program using Student's t-test.
 RESULTS: It was found that the most pronounced anxiolytic effect on rats with autism was exerted by the compound 2-[(diphenylphosphoryl)acetyl]-N-phenylhydrazine-1-carbothioamide (T8), increasing by 4.8 times (p=0.033) in females and 4.4 times (p=0.036) in males, the time they spent in open arms in the “Elevated Plus Maze” test. The corrective effect on social behavior in rats with autism was most noted for T8 and B2 [2-ethoxy-2-oxoethanammonium salt (2-ethoxy-2-oxotyl) phenylphosphinic acid], which was characterized by an increase in the time spent with a social object (unfamiliar rat) 6.4 times (p=0.04) and 5.2 times (p=0.039), respectively, in the “Extended open field” method. When assessing the behavior of rats in the valproate model of autism in the “Burying Balls” test, it was found that the use of B2, T8 and C5 reduced the level of stereotypy, reducing the number of buried balls by 1.7 times (p=0.009), 1.5 times (p=0.046 ) and 1.7 times (p=0.011), respectively, compared to rats in the valproate model of autism without treatment.
 CONCLUSION: Derivatives of phosphorylated acetohydrazides and thiosemicarbazide have an anxiolytic effect, correct disturbances in social behavior and reduce the severity of stereotypic behavior in rats in the valproate model of autism.

Synergistic Extraction of Erbium(III) by n-Octyl Phenyl Phosphinic Acid (OPPA) with Oxine and 2-Methyl Oxine in Different Diluents

The synergistic extraction of erbium (III) was investigated using n-octyl phenyl phosphinic acid (OPPA) in combination with oxine and 2-methyl oxine in different diluents. The extraction efficiencies of these synergistic extractants for erbium were measured as a function of extractant concentration, pH, temperature and diluents. The composition of extracted species determined by slope analysis method indicates the formation of [Er(HA2)3(HOX)]org complex and was also confirmed by Infrared spectroscopy. Based on the experimental data, the values of the equilibrium constants as well as synergistic coefficients have been calculated. Both the donors (oxine/2-methyl oxines) exhibited almost similar synergistic effect with OPPA. The extraction of erbium with these solvents was exothermic in nature. Diluent dependency on synergism for OPPA-oxine/2-methyl oxine system was explained in terms of regular solution theory of Hildebrand. Experimentally determined solubility parameter of ternary adduct was correlated with theoretically obtained values.

A SEM-EDX Study on the Structure of Phenyl Phosphinic Hybrids Containing Boron and Zirconium.

The SEM-EDX method was used to investigate the structure and morphology of organic-inorganic hybrids containing zirconium, boron and phosphorus compounds, synthesized by the sol-gel method. We started by using, for the first time together, zirconyl chloride hexa-hydrate (ZrOCl2·6H2O), phenyl phosphinic acid and triethyl borate as precursors and reagents, at different molar ratios. The obtained hybrids showed a very high thermal stability and are not soluble in water or in organic solvents. As a consequence, such hybrid solid materials are suitable for applications at high temperatures. The obtained hybrids have complex 3D structures and form organic-inorganic networks containing Zr-O-Zr, Zr-O-P and Zr-O-B bridges. Such organic-inorganic networks are also expected to form supramolecular structures and to have many potential applications in different fields of great interest such as catalysis, medicine, agriculture, energy storage, fuel cells, sensors, electrochemical devices and supramolecular chemistry.

Fabrication of a novelPNflame retardant and its synergistic flame retardancy with expandable graphite on rigid polyurethane foam

AbstractAn innovative phosphorus‐nitrogen flame retardant (ZrMP) is fabricated by reacting a‐zirconium phosphate (a‐ZrP), phenylphosphinic acid with melamine, and applied to improve the flame retardancy of rigid polyurethane foam/expandable graphite (RPUF/EG) composites. The synergistic effect of ZrMP and EG on the flame retardancy and thermal stability of RPUF was examined by the limiting oxygen index (LOI), UL‐94 vertical burning test, and thermogravimetric analyses. Benefiting from the P and N elements of ZrMP and the expanded char layer of EG, the synergistic effect of ZrMP and EG endows FPUF with excellent flame retardant and thermal properties. The RPUF composites containing 12.5% EG and 2.5% ZrMP can achieve a V‐0 level and its LOI value increases to 26.7%. RPUF/EG/ZrMP composites exhibit good thermal stability compared with pure RPUF. Accordingly, the flame‐retardant mechanism of RPUF composites is proposed by thermogravimetric analyses/infrared, scanning electron microscopy, and X‐ray photoelectron spectroscopy. The results indicate a combination of physical barriers in condensed‐phase and gaseous‐phase dilution activity during combustion. Therefore, this study provides a scalable and promising strategy for constructing flame‐retardant RPUF composites.

Oxidation Kinetics of some Lower Oxyacids of Phosphorus by Picolinium Chlorochromate: Determination of Reactive Reducing Species

Picolinium chlorochromate (PICC) in dimethylsuloxide (DMSO) oxidizes lower oxyacids of phosphorus, forming matching oxyacids with phosphorus in a higher oxidation state. The reaction shows a stoichiometry of 1:1. In relation to PICC, the response is first order. Regarding the reductants, a kinetics of the Michaelis-Menten type was noticed. Acrylonitrile does not undergo polymerization as a result of the reaction. Hydrogen ions function as catalysts for reactions. The form of the hydrogen-ion dependency is: kobs = a + b[H+]. Deuterated phosphinic and phenylphosphinic acids showed a significant primary kinetic isotope impact during oxidation. Nineteen different organic solvents were used to study the oxidation. The multiparametric equations of Taft and Swain were used to analyze the solvent effects. The influence of the solvent shows that the polarity of the solvent is crucial to the process. The penta-coordinated tautomer of the phosphorus oxyacid has been shown to be the reactive reductant, and it has been determined that the tricoordinated forms of phosphorus oxyacids do not take part in the oxidation process. It has been hypothesized that the rate-determining phase involves the transfer of a hydride ion.

Leaching NCM cathode materials of spent lithium-ion batteries with phosphate acid-based deep eutectic solvent

Deep eutectic solvents (DESs) play an important role in efficient recovery of spent lithium-ion batteries (LIBs). In this study, we proposed an efficient and safe method by using a choline chloride-phenylphosphinic acid DES as a lixiviant for the leaching of LiNixCoyMnzO2 (NCM) cathode active materials of spent LIBs. The leaching conditions were optimized based on the leaching time, liquid–solid ratio, and leaching temperature. Under optimal experimental conditions, the leaching efficiencies of Li, Co, Ni, and Mn reached 97.7 %, 97.0 %, 96.4 %, and 93.0 %, respectively. The kinetics of the leaching process were well-fitted using the logarithmic law equation. The apparent activation energies for Li, Co, Ni, and Mn have been reported to be 60.3 kJ/mol, 78.9 kJ/mol, 99.3 kJ/mol, and 82.1 kJ/mol, respectively. UV–visible spectroscopy and Fourier transform infrared analysis revealed that the coordination configurations of Ni and Co in the leaching solution were octahedral and tetrahedral, respectively. In addition, the PO bond in phenylphosphinic acid was involved in coordination during leaching. This finding may provide an effective and safe approach for leaching valuable metals from spent LIBs.

New Efficient Synthesis of 6,12-Dihydro-5H-quinazolino[3,2-a] quinazolin-5-ones via Ugi/Staudinger/Aza-Wittig/Addition/Nucleophilic Acyl Substitution Sequence

AbstractA new efficient synthesis of 6,12-dihydro-5H-quinazolino[3,2-a]quinazolin-5-ones by sequential Ugi/Staudinger/aza-Wittig/addition/nucleophilic acyl substitution has been developed. α-Amino amides, obtained from Ugi-3CR of 2-azidobenzaldehydes, methyl 2-aminobenzoates, and isocyanides in the presence of catalytic amount of phenylphosphinic acid, reacted with triphenylphosphine and isocyanates to give 6,12-dihydro-5H-quinazolino[3,2-a]quinazolin-5-ones in good yields. This method provides a domino and effective strategy for the preparation of various substituted quinazolino[3,2-a]quinazolin-5-ones under mild reaction condition.

Fire-safe and tough semi-aromatic polyamide enabled by halloysite-based self-assembled microrods

High performance flame-retardant engineering plastics are highly desirable in electronic appliances, automotive industry, and aerospace fields. However, traditional flame retardants usually lead to impaired intrinsic properties of plastics, especially mechanical properties. Here, we present a hybrid flame retardant with unique hierarchical microrod structure via self-assembly of halloysite nanotube loaded with phenylphosphinic acid. The resultant hybrid integrates excellent thermal stability (Td = 406 °C), interfacial adhesion, and superior flame-retardant efficiency, that endows semi-aromatic polyamide great mechanical properties (tensile strength 67.3 MPa and 73.2 MPa)，improving by 27% and 38% via 5 wt% and 10 wt% addition, compared to that of pristine resin, and excellent flame retardancy with anti-dripping and self-extinguishing (UL-94 V-0, LOI 30.4%) via 10 wt% addition. Meanwhile this hybrid is demonstrated, with 5 wt% or 10 wt% addition of self-assembly halloysite, the composites can form an effective char barrier, that emphasize its fire-safety properties in simulating fire scenario via approximately halving peak of heat release rate and peak of carbon monoxide release rate of the composites. This self-assembly strategy outlined here paves a novel and facile approach for fabrication and widely application of high performance fire-safety polyamides. This will largely improve the reliability of materials in service, reduce the fire probability of electronic devices and casualties caused by fire.

SERS/TERS Characterization of New Potential Therapeutics: The Influence of Positional Isomerism, Interface Type, Oxidation State of Copper, and Incubation Time on Adsorption on the Surface of Copper(I) and (II) Oxide Nanoparticles.

The aim of this study was to investigate how the oxidation state of copper (Cu(I) vs Cu(II)), the nature of the interface (solid/aqueous vs solid/air), positional isomerism, and incubation time affect the functionalization of the surface of copper oxide nanostructures by [(butylamino)(pyridine)methyl]phenylphosphinic acid (PyPA). For this purpose, 2-, 3-, and 4-isomers of PyPA and the nanostructures were synthesized. The nanostructure were characterized by UV-visible spectroscopy (UV–vis), scanning electron microscopy (SEM), Raman spectroscopy (RS), and X-ray diffraction (XRD) analysis, which proved the formation of spherical Cu2O nanoparticles (Cu2ONPs; 1500–600 nm) and leaf-like CuO nanostructures (CuONSs; 80–180/400–700 nm, width/length). PyPA isomers were deposited on the surface of NSs, and adsorption was investigated by surface-enhanced Raman scattering (SERS) and tip-enhanced Raman scattering (TERS). The changes of adsorption on the surface of copper oxide NSs caused by the above-mentioned factors were described and the enhancement factor on this substrate was calculated.

Immobilization of an organophosphorus compound on polypropylene‐g‐poly(glycidyl methacrylate) polymer support and its application in scandium recovery

AbstractScandium is a rare earth element that has a wide range of uses in modern technology. The conventional recovery of scandium is commonly done by solvent extraction using organophosphorus compounds. This process however produces a lot of waste extractants. To circumvent this challenge, a model organophosphorus compound phenylphosphinic acid (PPI) was immobilized to a polymer support fabric to produce a Sc(III) adsorbent for high throughput scandium recovery with less waste generation. Polymer support (PP‐g‐PGMA) for the organophosphorus compound was synthesized using radiation‐induced graft polymerization. Successful post‐polymer modification of the PGMA grafts to attach PPI groups was carried out using 1 M PPI in isopropanol at 80°C for 4 h, achieving a maximum functional group density of 1.32 mmol/g. The obtained PP‐g‐PGMA‐PPI fabrics were used in the batch Sc(III) adsorption experiments. The results showed that PP‐g‐PGMA‐PPI effectively adsorbed low concentrations of Sc(III) at a pH of at least 2.0. More than 98% adsorption was achieved using 1 ppm Sc(III). The synthesized adsorbent was also shown to be selective for Sc(III) even in the presence of Fe(III) and Al(III) ions. PP‐g‐PGMA‐PPI adsorbent fabrics are therefore promising alternatives to solvent extraction methods and ion‐exchange granular resin technologies in the recovery of scandium.

NMR Quantification of Hydrogen-Bond-Accepting Ability for Organic Molecules.

The hydrogen-bond-accepting abilities for more than 100 organic molecules are quantified using 19F and 31P NMR spectroscopy with pentafluorobenzoic acid (PFBA) and phenylphosphinic acid (PPA) as commercially available, inexpensive probes. Analysis of pyridines and anilines with a variety of electronic modifications demonstrates that changes in NMR shifts can predict the secondary effects that contribute to H-bond-accepting ability, establishing the ability of PFBA and PPA binding to predict electronic trends. The H-bond-accepting abilities of various metal-chelating ligands and organocatalysts are also quantified. The measured Δδ(31P) and Δδp(19F) values correlate strongly with Hammett parameters, pKa of the protonated HBA, and proton-transfer basicity (pKBH+).

Grafting on metal oxide surface of phenyl phosphinic acid by using solid-state process

The present work describes the synthesis of novel hybrid materials by grafting process of phenyl phosphinic acid on different metal oxide surfaces (V2O5, ZrO2 and SnO2), by using a reactive milling process. Therefore, the syntheses took place in the solid phase, avoiding the presence of solvents. The grafting of the metal oxide surface is performed by using phenyl phosphinic acid as the coupling agent. After the syntheses in the solid phase were finished, the grafted materials were further characterized by FTIR, TGA, SEM and EDX methods. While phenyl phosphinic acid is water-soluble, the synthesized hybrids are insoluble in water. Moreover, from TGA results, it can be observed that the thermal stability increased significantly for the obtained hybrids in comparison with the starting reagents. In addition, the EDX data confirmed the presence of phosphorus, as well as the presence of the used metals (Zr, V and Sn).

Sensitivity of 31 P NMR chemical shifts to hydrogen bond geometry and molecular conformation for complexes of phosphinic acids with pyridines.

The results of the quantum-chemical investigation of a series of hydrogen-bonded 1:1 acid-base complexes formed by model phosphinic acids, Me2 POOH, and PhHPOOH, are reported. A series of substituted pyridines (pKa range from 0.5 to 10) was chosen as proton acceptors. Gradual changes of isotropic 31 P nuclear magnetic resonance (NMR) chemical shift, δP, were correlated with the bridging proton position in the intermolecular OHN hydrogen bond, namely, r (OH) distance; the proposed correlation could easily be extended to other phosphinic acids as well. For complexes with pyridine and 2,4,6-trimethylpyridine, we have investigated in more detail several factors influencing the δP values: (1) the proton transfer within the OHN hydrogen bond; (2) the rotation of the pyridine ring around the hydrogen bond axis (associated with the formation/breakage of additional weak PO···H-C hydrogen bond); and (3) the rotation of the phenyl substituent in phenylphosphinic acid around the P-C axis. All these factors appeared to be of similar magnitude, thus masking their individual contributions that have to be independently estimated for a reliable spectral interpretation.

Kinetic study on the synergistic effect between molecular weight and phosphorus content of flame retardant copolyesters in solid‐state polymerization

Abstract2‐Carboxyethyl(phenyl phosphinic) acid has been proved to modify flame retardant properties of poly(ethylene terephthalate) (PET) through copolymerization; however, there is no industrial technological breakthroughs in polyester industrial yarns which requires high strength and modulus, because it is related to the coordinated control of molecular weight and flame retardancy. In this work, the influence of solid‐state polymerization reaction kinetics and parameters on flame retardancy retention have been investigated, based on the prepared precursors optimized at 6,000 ppm phosphorus content and 0.64 dL/g intrinsic viscosity (I.V). Results showed that the copolyester polydispersity index increase was significant compared to PET with molecular weight increase. The I.V of optimized precursor could be increased to 1.31 dL/g at 220°C in 20 hr, but at higher phosphorus content loses up to 7%. Flame retardant component deteriorates with increasing reaction rate and temperature as a result of severe side reactions. Optimized precursor at the optimum temperature (210°C) reacted for 20 hr, copolyester with the phosphorus content of 5,910 ppm and the I.V of 1.12 dL/g (( was about 3.5 × 104 g/mol) was prepared. The coordination between high molecular weight and flame retardant performance was realized.

A new diphosphonic acid extractant N,N-n-octylamine di(methylene phenylphosphinic acid) for extraction and separation of zirconium and hafnium in hydrochloric acid

Nuclear grade zirconium and hafnium are the key to promoting the development of nuclear industry. We designed and synthesized a new diphosphonic acid extractant N,N-n-octylamine di(methylene phenylphosphinic acid) (OADMPPA) with excellent extraction ability and priority for extraction of zirconium. This paper focused on the changes in extraction mechanisms and composition of complexes. With increasing concentration of HCl, cation exchange mechanism gradually changed into solvation mechanism, and complexes converted in the order of ZrOA, Zr(HA)2Cl2 and ZrCl4·H2A. Compared with bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex272), OADMPPA could increase the extraction rates of zirconium and hafnium by 7.2 and 12.6 times.

Ni-Catalyzed asymmetric reduction of α-keto-β-lactams via DKR enabled by proton shuttling.

Chiral α-hydroxy-β-lactams are key fragments of many bioactive compounds and antibiotics, and the development of efficient synthetic methods for these compounds is of great value. The highly enantioselective dynamic kinetic resolution (DKR) of α-keto-β-lactams was realized via a novel proton shuttling strategy. A wide range of α-keto-β-lactams were reduced efficiently and enantioselectively by Ni-catalyzed asymmetric hydrogenation, providing the corresponding α-hydroxy-β-lactam derivatives with high yields and enantioselectivities (up to 92% yield, up to 94% ee). Deuterium-labelling experiments indicate that phenylphosphinic acid plays a pivotal role in the DKR of α-keto-β-lactams by promoting the enolization process. The synthetic potential of this protocol was demonstrated by its application in the synthesis of a key intermediate of Taxol and (+)-epi-Cytoxazone.